Dyestuffs of the anthraquinone series containing dichloropyrimidyl



United States Patent 0.

This invention relates to dyestuffs of the anthraquinone series whichcontain reactive groups and correspond to the formula:

wherein A stands for hydrogen or a low molecular alkyl radical, H

R for an aryl radical which may be substituted,

R for a phenyl radical which may be substituted,

X for oxygen and Y for the amino or, together with X, for the groupingin which R represents a low molecular carbalkoxy radical, a lowmolecular alkylcarbonyl radical or a phenylcarbonyl radical which may besubstituted, and

R represents the hydroxy group, a low molecular alkyl radical or aphenyl radical which may be substituted, when R denotes a low molecularcarbalkoxy radical, or represents the hydroxy group, when R denotes alow molecular alkylcarbonyl radical or a phenylcarbonyl radical whichmay be substituted.

Z for the radical of a cyclic, six-membered diazine compound containingtwo or three halogen atoms combined with carbon atoms, and

n for one of the integers 2 or 3,

and wherein the group stands in the para-position to NH-.

The process for their production consists in reacting 1 mole of adyestutl oi the formula Patented May 15., 1 962 "ice 2 wherein A, R, RX, Y and n possess the aforeci'ted meanings and wherein the group H isin para-position to the NH group, with at least 1 mole of a cyclic,six-membered diazine compound containing three or four halogen atomscombined with carbon atoms.

The dyestufis of Formula II which are used as starting substances areeither l-aminoanthraquinone.derivatives or 3-azabenzanthronederivatives. Particularly intercsting representatives of thel-aminoanthraquinone compounds are, i.e. l-amino-2-(4-methyl)-,-(4'-ethyl)-., -(4'-tert.hutyl)-, -(4'-tert.amyl)- or-(4-iso-octyl)-phenoXy-4(4"-amino)- or-(4methylamino)-phenylaminoanthraquinone-Z'.2-disulfonic acid,1-amino-2-(S'-methyl)-phenoXy-4-(4-amino) phenylamino-anthraquinone2'.2"-disulfonic acid, l-amino-2-(4'-methyl)-phenoxy-4-[(4-arnino)-phenyl]-phenylaminoanthraquinone-Z.2"- or 2.2"-disulfonicacid. 1 I

Of the 3-azabenzanthrone derivatives the following may be named asexamples: l-benzoylor l-acetylor l-carbethoxyor1-carbomethoxy-Z-hydroxy-4-phenoxy- 6- (4"amino or (4-methylamino-phenylaminc-3-azabenzanthrone-4'.2 dior -2'.4.2"-trisulfonic acid, 1-.acetylor -1-benz0ylor 1-carbethoxy-2-hydroXy-4-(4'- or S-methyD- or-(4'-tert. butyl)- or -(4-tert. amyl) or-(4-iso-octyl)-phenoxy-6-(4"-amino)- or -(4"-methylamino)phenylamino-3-azabenzanthrone-2.2"-disulfonic acid, l-acetylorl-benzoylor 1-carbethoxy-2-hydroxy- 4-phenoXy-6-[4"-(4"'-amino)phenyl]-phenylamino-3- azabenzanthrone-4'.2- or -4.2'-di or -2'.4'.2"-or -2'.4.2"-trisulfonic acid, l-carbethoxy 2 methylor-phenyl-4-phenoxy-6- (4-amino or (4"-methylaminophenylamino-3-azabenzanthrone-4.2"-dior -2'.4.2-trisulfonic acid,l-carbethoxyor l-carbomethoXy-2-methylor -phenyl-4-(4'-methy1)- or-(4'-ethyl)- or -(4-tert.

(4"-amino)- or-(4"-methylamino)-phenylamino-3-azabenzanthrone-Z'.2-disulfonic acid,l-carbethoxy-Z-methylor -phenyl-4-(4'-methyl)-phenoxy-6-[4"-(4"-amino)-phenyl]-phenylamino-3-azabenzanthrone-2.2- or 2.2- disulfonic acid.Trichloropyrimidine, .tribromopyrim idine and tetrachloropyrimidine areexamples of diazine compounds coming within the scope of the presentprocess.

The reaction of the dyestuils of Formula II used as starting substanceswith a cyclic, six-membered diazine compound containing three or fourhalogen atoms combined with carbon atoms is carried out preferably inaqueous medium. For this purpose the trihalogenoor.tetrahalogeno-diazine compound may be applied as such .in concentratedform or in solution in an organic solvent. Acetone is an outstandinglysuitable solvent.

The reaction temperature is adapted to the reactivity of the individualstarting substances and varies between 40 and C. If it is desired toconduct the reaction at temperatures above 50-60 C., it is advisable .towork in closed vessels fitted with reflux condensers.

The reaction is effected in a weakly alkaline medium,

preferably within the pH region of 10.0 to 7.0. T o neutralize thehydrogen halide formed an acid-binding agent such as sodium or ammoniumacetate may be added at,

In the reaction of the trihalogenoor tetrahalogenodiazine compound withthe -NH-A group only one halogen atom reacts with an exchangeablehydrogen atom.

On completion of condensation the dyestulf formed is salted out from thepreviously neutralized solution or suspension with sodium or potassiumchloride or precipitated with an acid. It is then filtered with suction,Washed neutral, and dried.

The dyestuffs obtained in accordance with the present process aresuitable for dyeing, padding and printing fibers of vegetable and animalorigin, fibers of regenerated cellulose, casein fibers, animalizedcellulosic fibers, polyamide fibers, mixtures of the preceding fibers,and leather. The dyed material is treated in the dyebath or in asubsequent operation with an agent of alkaline reaction with heating.The dyeings possess good fastness to light, washing, milling andperspiration. Polyester fibers, secondary cellulose acetate andcellulose triacetate are reserved.

In the following examples the parts and percentages are by Weight andthe temperatures are in degrees centigrade.

EXAMPLE 1 66.5 parts of the dyestuif 1-amino-2-(4'-tert.amyl)- phenoxy 4(4"-methylamino)-phenylaminoanthraquinone-2'.2"-disulfonic acid aredissolved in 1000 parts of water with about 25 parts of a 30% sodiumhydroxyde solution to give a neutral reaction. After the addition of 20parts of trichloropyrimidine the temperature is increased to 80 withvigorous agitation. The pH value is maintained between 8.0 and 9.0 bythe addition of a 10% sodium carbonate solution.

When the condensation reaction has run its course 100 parts of sodiumchloride are strewn into the solution, upon which the new dyestufi isprecipitated. 'It is filtered off, washed with a dilute aqueous solutionof sodium chloride, and dried in vacuo at 50-60". The dark powderobtained dissolves in water to give violet solutions.

On padding a cellulosic fiber fabric with an aqueous solution of thisdyestutf and heat-treating the padding in presence of an agent ofalkaline reaction, a bluish violet dyeing fast to light and wettreatments is obtained.

Table 1 below lists further dyestuffs containing re active groups whichcan be produced by the process described in Example 1. These dyestuffshave the formula O-Rl ll NET-R4 .To simplify the nomenclature theabbreviations DDZ and TDZ respectively are used for thedichloropyrimidyl radical and the trichloro pyrimidyl radical.

4 EXAMPLE 8 38.35 parts of sodium 1-benzoyl-2-hydroxy-4-(4- methyl)phenoxy 6 (4"-amino)-phenylamino-3-azabenzanthrone-Z.2f'-disulfonate aredissolved in 1000 parts of water at 60. 10 parts of trichloropyrimidineare added, the temperature increased to and a pH value of between 8.0and 9.0 is maintained by addition of a 10% sodium carbonate solution.The mass is stirred until such time as the starting substance is nolonger indicated in a sample by chromatography on a talc column.

The dyestuffs is precipitated by means of 100 parts of common salt,filtered off and dried in vacuo.

100 parts of a cotton sateen fabric are padded at room temperature witha 2% aqueous neutral solution of the above dyestuif in presence of lgram per liter of turkey red oil, and squeezed to 1.6 to 2.2 times itsoriginal dry weight. The moist fabric is treated in a developing bath(liquor ratio 50: 1) containing 300 grams per liter of common salt and 5ml. per liter of sodium hydroxide solution of 66 Tw. (36 B.) for 20-30minutes at 95. It is then thoroughly rinsed in cold water, s'oaped atthe boil for 20 minutes with 5 grams per liter of soap and 2 grams perliter of sodium bicarbonate (liquor ratio 20:1), again Well rinsed, anddried. A violet dyeing fast to light and wet treatments is obtained.

EXAMPLE 9 33.75 parts of l-carbethoxy-2-methyl-4-phenoxy-6-(4"-amino)-phenylamino-3-azabenzanthrone 4.2" disulfonic acid aredissolved in 1000 parts of water and 14 parts of a 30% sodium hydroxidesolution at 60". At the same temperature 25 parts oftetrachloro-pyrimidine are added in small portions and simultaneously a10% sodium carbonate solution is added dropwise to the solution tomaintain the pH value of 8.0 to 9.0. The temperature is then increasedto 80. The reaction is com pleted when the starting substance is nolonger indicated in a sample. The dyestuff is precipitated with parts ofsodium chloride, filtered off, washed with brine until neutral reaction,and finally dried in vacuo at 50-60". A powder is obtained which issoluble in water with an orange-red coloration and dyes natural andregenerated cellulosic fibers from weakly alkaline dyebaths inorange-red shades which are fast to light and wet treatments.

In Table 2 are listed a number of dyestuffs containing reactive groupsWhich are obtainable according to the processes of Examples 8 and 9.They correspond to the formula and TDZ respectively are used fo'r thedichloropyrimidyl radical and the trichloropyrimidal radical.

Table 2 Example R; R1 R1 R1 Shade of Dyeing on Cotton 10 hydroxy acetyl4-1soctyl-2-sul1'ophenoxy -4. 4-DDZ-amtno-2"-sulfophenylamlno violetishred.

11 do carbethoxy 4-methyl-2-sultophenoxy.--.4-DDZ-(N-methy1)-anim0-2-sul- Do.

fophenylamlno.

12 do benzoyl 2C4 disulfophenoxy 4[(4-DDZ-amino)-phenyl]-2-sulreddishviolet.

tophenylamlno 13 do -d 4'-t.amyl-2'-su1iophenoxy-DDZ-am1n0-2-su1fophenylamino violetish red.

14 do., carbethoxyun d0 4-TDZ-(N-methyl)-amino-2-su1- Do.

fophenylamino.

15 methyl ...-d0 4-methly-2-sulfophenoxy-DDZ-(N-methyl)-amino-2-sulorange red.

tophenylamino.

16 do "do 4Ms00ctyl-2'sulf0phenoxy. 4-DDZ-amino-2"-sulfophenylamine Do.

17 pheny l do 2,4-dlsuliophenoxy 4"DDZ-(N-methyl)-amino-2-sul- Do.

tophenylamino.

18 methy1 carbomethoxy 4'-t.amyl-2-suliophenoxy4"-[4-DDZ-aminopheny1]-2-sulred.

tophenylamlno.

. 4-n-heptyl-2-sulfophenoxy Do. 4-n-hexyl-2-sy1tophenoxyin D0.

phenylamino. 4'-tertomyl-T-sulfophenoxm.- do Do.4-lsopropyl-2'-sulfophenoxy 4-TDZ-amino-2"-suliophenylamlno. D0.

Formulae of representative dyestuffs of the foregoing Example 11--examples are:

Example l OH O NH: 30:11 a! i] i HaCz-OOC- N 30511 O t u tart.

O CH,

SOzH

CH; SOgH ll 0H. 0 NH N 0 NH N DDZ DDZ

DDZ=radical of dichloropyrimidine Exam le 24- Exarnple 3- p O NHfi $03Kl l 7 EH -OC -C4Hw tert.

O-co- N so n SOzH ll 0 aHu. WM. 0 NH-O-NH-DHZ 25 SIOZH CH l Example 8- INH-- N\ DDZ C 50 H Y I Having thus disclosed the invention what I claimis:

1. An anthraquinone dyestuff of the formula 0 1 SO H A ii i i N R D 80 H0 NIL-ONH-DDZ Exam 1e 9 p 40 wherein e" c A is a member selected fromthe group consisting of N hydrogen and lower alkyl;

I l R is a member selected from the group consisting of C phenylene andbiphenylene,

Z is a member selected from the group consisting of S031;dichloropyrimidyl and trichloropyrimidyl, wherein the H l chlorine atomsand the group -NA-- are each bound 0 NHC NH DD to a carbon atom of thepyrimidine ring;

n is an integer ranging from 2 to 3; and

D is a member selected from the group consisting of c v. 9 NH, v w Bl C)NH- wherein R is a member selected from the group consisting of 2. The

anthraquinone dyestufr' of the formula NH; 503E SOaH dichloropyrimidyl3. The anthraquinone dyestutf of the formula SO H NH--NH-dichloropyrimidyl 4. The anthraquinone d yestulf of the formulaphenyl and alkylphenyl wherein alkyl has from 1 to 8 50 carbon atoms;

R is a member selected from the group consisting of carbomethoxy andcarboethoxy;

R;, is a member selected from the group consisting of acetyl andbenzoyl, and

NH NH-dlchloropyrlmidyl 5. The anthraquinone dyestuff of the formulaHsCn-OOC-l N SIOIH SOiH CH:

NH N diehloropyrimldyl 6. The anthraquinone dyestufi of the formulaO-CsHn-tertiary SO H NH- N dichloropyrimidyl R is a member selected fromthe group consisting of methyl and ph yl;

group References Cited in the file of this patent UNITED STATES PATENTSPeter et al Dec. 25, 1951 Bucheler et al Aug. 21, 1956 Brassel etal Dec.11, 1956 a '1 FOREIGN PATENTS Great Britain May 19, 1931 UNITED STATESPATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,035,058 May 15 1962Jacques Guenthard It is hereby certified that error appears in the abovenumbered patent requiring correction and that the said Letters Patentshould read as corrected below.

Column l lines 54 to 57, the formula should appear as shown belowinstead of as in the patent:

column 3, line 29, for "hydroxyde" read hydroxide column 4, lines 57 to66, lower right-hand portion of the formula for I NH-R read NIT-R column5, lines 19 to 25, lower right-hand portion of the formula, for "NH-DHZ"read -NHDDZ Signed and sealed this 20th day of November 1962.

(SEAL) Attest:

ERNEST W. SWIDER DAVID L. LADD Attesting Officer Commissioner of Patents

1. AN ANTHRAQUINONE DYESTUFF OF THE FORMULA